Compositions based on 2,3,3,4,4,4-hexafluorobut-1-ene

ABSTRACT

A composition including 2,3,3,4,4,4-hexafluorobut-1-ene as a mixture with one or more hydrocarbon, hydrofluorocarbon, ether, hydrofluoroether or fluoroolefin compounds having a boiling point of less than or equal to 0° C. Also, the use of such a composition in heat transfer applications. Also, a heat transfer installation including a vapor compression circuit containing such a composition as heat-transfer fluid or containing a heat-transfer composition including such a composition, and also one or more additives chosen from lubricants, stabilizers, surfactants, tracers, fluorescers, odorous agents and solubilizers, and mixtures thereof.

FIELD OF THE INVENTION

The present invention relates to compositions based on2,3,3,4,4,4-hexafluorobut-1-ene, and also to their use especially asheat-transfer fluids.

TECHNICAL BACKGROUND

Fluids based on fluorocarbon compounds are widely used invapor-compression heat-transfer systems, especially air-conditioning,heat pump, refrigeration or freezing devices. The common feature ofthese devices is that they are based on a thermodynamic cycle comprisingvaporization of fluid at low pressure (in which the fluid absorbs heat);the compression of the vaporized fluid up to a high pressure; thecondensation of the vaporized fluid to liquid at high pressure (in whichthe fluid expels heat); and the depressurization of the fluid tocomplete the cycle.

The choice of a heat-transfer fluid (which may be a pure compound or amixture of compounds) is dictated firstly by the thermodynamicproperties of the fluid, and secondly by additional constraints. Thus, aparticularly important criterion is that of the impact of the fluidunder consideration on the environment. In particular, chlorinatedcompounds (chlorofluorocarbons and hydrochlorofluorocarbons) have thedrawback of damaging the ozone layer. Non-chlorinated compounds such ashydrofluorocarbons, fluoro ethers and fluoroolefins are thus nowgenerally preferred.

It is, however, necessary to develop other heat-transfer fluids thathave a lower global warming potential (GWP) than that of theheat-transfer fluids currently used, and which have equivalent orimproved performance qualities.

Document US 2009/0 143 604 describes processes for manufacturing fluoroalkanols and fluoroolefins. The synthesis of2,3,3,4,4,4-hexafluorobut-1-ene (HFO-1336yf) is especially disclosed.

Document WO 2009/085 937 describes a secondary cooling loop system foran air conditioning system. Among the heat-transfer compounds that maybe used is HFO-1336yf.

Document US 2009/0 302 264 describes heat-transfer compositionscomprising a heat-transfer fluid, a lubricant and an acidic deactivator.HFO-1336yf is cited among the possible heat-transfer fluids.

Document US 2011/0 088 418 describes compositions comprising an ionicliquid and a fluoroolefin, which are useful for heat-transferapplications with absorption systems. HFO-1336yf is cited as an exampleof a fluoroolefin.

However, there is still a need to develop other heat-transfer fluidsthat have a relatively low GWP, and that are capable of replacing theusual heat-transfer fluids.

In particular, it is desirable to develop other low-GWP heat-transferfluids that are quasi-azeotropic and/or that have good energyperformance qualities when compared with the usual heat-transfer fluids(such as isobutane) and/or energy performance qualities that are betterthan those of the known low-GWP heat-transfer fluids.

SUMMARY OF THE INVENTION

The invention relates first to a composition comprising2,3,3,4,4,4-hexafluorobut-1-ene as a mixture with one or morehydrocarbon, hydrofluorocarbon, ether, hydrofluoroether or fluoroolefincompounds with a boiling point of less than or equal to 0° C.

According to one embodiment, the composition consists of a mixture of2,3,3,4,4,4-hexafluorobut-1-ene and of one or more hydrocarbon,hydrofluorocarbon, ether, hydrofluoroether or fluoroolefin compoundswith a boiling point of less than or equal to 0° C.

According to one embodiment, the composition is a binary mixture ofcompounds; or is a ternary mixture of compounds.

According to one embodiment, the composition is a binary mixture of2,3,3,4,4,4-hexafluorobut-1-ene with a hydrocarbon, hydrofluorocarbon,ether, hydrofluoroether or fluoroolefin compound with a boiling point ofless than or equal to 0° C.; or is a ternary mixture of2,3,3,4,4,4-hexafluorobut-1-ene with a first hydrocarbon,hydrofluorocarbon, ether, hydrofluoroether or fluoroolefin compound witha boiling point of less than or equal to 0° C. and with a secondhydrocarbon, hydrofluorocarbon, ether, hydrofluoroether or fluoroolefincompound with a boiling point of less than or equal to 0° C.

According to one embodiment, the hydrocarbon, hydrofluorocarbon, ether,hydrofluoroether or fluoroolefin compound(s) with a boiling point ofless than or equal to 0° C. have a boiling point of less than or equalto −5° C. and preferably less than or equal to −10° C.

According to one embodiment, the hydrocarbon, hydrofluorocarbon, ether,hydrofluoroether or fluoroolefin compound(s) with a boiling point ofless than or equal to 0° C. are chosen from 1,3,3,3-tetrafluoropropene,2,3,3,3-tetrafluoropropene, 1,1,3,3-tetrafluoropropene,3,3,3-trifluoropropene, 2,3,3-trifluoropropene,1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, pentafluoroethane,1,1,1,2,3,3,3-heptafluoropropane, 1,1-difluoroethane,1,1,1-trifluoropropane, isobutane and propane, and mixtures thereof.

According to one embodiment, the hydrocarbon, hydrofluorocarbon, ether,hydrofluoroether or fluoroolefin compound(s) with a boiling point ofless than or equal to 0° C. are chosen from 1,3,3,3-tetrafluoropropene,2,3,3,3-tetrafluoropropene, 1,1,1,2-tetrafluoroethane,1,1,2,2-tetrafluoroethane, 1,1-difluoroethane and1,1,1-trifluoropropane, and mixtures thereof.

According to one embodiment, the composition comprises or preferablyconsists of:

-   -   a mixture of 2,3,3,4,4,4-hexafluorobut-1-ene and        1,3,3,3-tetrafluoropropene; or    -   a mixture of 2,3,3,4,4,4-hexafluorobut-1-ene and        1,1,1-trifluoropropane; or    -   a mixture of 2,3,3,4,4,4-hexafluorobut-1-ene and        1,1,2,2-tetrafluoroethane; or    -   a mixture of 2,3,3,4,4,4-hexafluorobut-1-ene and        1,1,1,2-tetrafluoroethane; or    -   a mixture of 2,3,3,4,4,4-hexafluorobut-1-ene and        1,1-difluoroethane; or    -   a mixture of 2,3,3,4,4,4-hexafluorobut-1-ene,        1,1,1,2-tetrafluoroethane and 1,3,3,3-tetrafluoropropene; or    -   a mixture of 2,3,3,4,4,4-hexafluorobut-1-ene,        1,1,1,2-tetrafluoroethane and 1,1,1-trifluoropropane;    -   a mixture of 2,3,3,4,4,4-hexafluorobut-1-ene,        1,1,1,2-tetrafluoroethane and 1,1-difluoroethane.    -   a mixture of 2,3,3,4,4,4-hexafluorobut-1-ene,        1,1,2,2-tetrafluoroethane and 1,3,3,3-tetrafluoropropene; or    -   a mixture of 2,3,3,4,4,4-hexafluorobut-1-ene,        1,1,2,2-tetrafluoroethane and 1,1,1-trifluoropropane.

According to one embodiment, the difference between the liquidsaturation pressure and the vapor saturation pressure at a temperatureof −5° C. is less than or equal to 10% of the liquid saturationpressure.

According to one embodiment, the composition is non-flammable.

The invention also relates to the use of the abovementioned compositionas a heat-transfer fluid.

The invention also relates to a heat-transfer composition, comprisingthe abovementioned composition as heat-transfer fluid, and also to oneor more additives chosen from lubricants, stabilizers, surfactants,tracers, fluorescers, odorant agents and solubilizers, and mixturesthereof.

The invention also relates to a heat-transfer installation comprising avapor compression circuit containing a composition as described above asheat-transfer fluid or containing a heat-transfer composition asdescribed above.

According to one embodiment, the installation is chosen from mobile orstationary heat-pump heating, air-conditioning, refrigeration, freezingand Rankine cycle installations, and is preferably a containerrefrigeration installation.

The invention also relates to a process for heating or cooling a fluidor a body by means of a vapor compression circuit containing aheat-transfer fluid, the said process comprising, successively,evaporation of the heat-transfer fluid, compression of the heat-transferfluid, condensation of the heat fluid and depressurization of theheat-transfer fluid, in which the heat-transfer fluid is a compositionas described above.

According to one embodiment, this process is a process for cooling afluid or a body, in which the temperature of the cooled fluid or body isfrom −15° C. to 15° C., preferably from −10° C. to 10° C. and moreparticularly preferably from −5° C. to 5° C.; or is a process forheating a fluid or a body, in which the temperature of the heated fluidor body is from 30° C. to 90° C., preferably from 35° C. to 60° C. andmore particularly preferably from 40° C. to 50° C.

The invention also relates to a process for reducing the environmentalimpact of a heat-transfer installation comprising a vapor compressioncircuit containing an initial heat-transfer fluid, the said processcomprising a step of replacing the initial heat-transfer fluid in thevapor compression circuit with a final transfer fluid, the finaltransfer fluid having a GWP lower than that of the initial heat-transferfluid, in which the final heat-transfer fluid is a composition asdescribed above.

The present invention makes it possible to overcome the drawbacks of theprior art. It more particularly provides low-GWP heat-transfer fluids,which can replace the usual heat-transfer fluids.

In particular, in certain embodiments, the invention providesquasi-azeotropic heat-transfer fluids. In certain embodiments, theinvention provides heat-transfer fluids which have good energyperformance qualities (especially volumetric capacity and/or coefficientof performance) when compared with usual heat-transfer fluids and/orwhich have improved energy performance qualities when compared with theknown low-GWP heat-transfer fluids.

This is accomplished by means of mixtures comprising, firstly,HFO-1336yf, and, secondly, at least one hydrocarbon, hydrofluorocarbonor fluoroolefin compound with a boiling point of less than or equal to0° C. and preferably less than or equal to −10° C., which is chosen inparticular from the list of compounds mentioned above.

Mixtures comprising compounds with a low boiling point have an improvedvolumetric capacity when compared with HFO-1336yf alone. The increase inthe volumetric capacity of a composition allows the use of compressorswith a smaller swept volume, and consequently a smaller size.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The invention is now described in greater detail and in a nonlimitingmanner in the description that follows.

The main compounds used in the context of the invention are noted asfollows:

-   -   2,3,3,4,4,4-hexafluorobut-1-ene: HFO-1336yf;    -   1,3,3,3-tetrafluoropropene: HFO-1234ze;    -   2,3,3,3-tetrafluoropropene: HFO-1234yf;    -   1,1,3,3-tetrafluoropropene: HFO-1234zc;    -   3,3,3-trifluoropropene: HFO-1243zf;    -   2,3,3-trifluoropropene: HFO-1243yf;    -   1,1,1,2-tetrafluoroethane: HFC-134a;    -   1,1,2,2-tetrafluoroethane: HFC-134;    -   pentafluoroethane: HFC-125;    -   1,1,1,2,3,3,3-heptafluoropropane: HFC-227ea;    -   1,1-difluoroethane: HFC-152a;    -   1,1,1-trifluoropropane: HFC-263fb;    -   propane: HC-290;    -   isobutane: HC-600a.

Unless otherwise mentioned, throughout the patent application, theproportions of compounds indicated are given as mass percentages.

HFO-1234ze may be in cis or trans form or may be a mixture of these twoforms. Preferably, it is in trans form (E).

According to the present patent application, the global warmingpotential (GWP) is defined relative to carbon dioxide and relative to aduration of 100 years, according to the method indicated in “Thescientific assessment of ozone depletion, 2002, a report of the WorldMeteorological Association's Global Ozone Research and MonitoringProject”.

The term “heat-transfer compound” or, respectively, “heat-transferfluid” (or cold-generating fluid) means a compound or, respectively, afluid that is capable of absorbing heat by evaporating at lowtemperature and low pressure and of expelling heat by condensing at hightemperature and high pressure, in a vapor compression circuit. Ingeneral, a heat-transfer fluid may comprise one, two, three or more thanthree heat-transfer compounds.

The term “heat-transfer composition” means a composition comprising aheat-transfer fluid and optionally one or more additives that are notheat-transfer compounds for the intended application.

The additives may be chosen especially from lubricants, nanoparticles,stabilizers, surfactants, tracers, fluorescers, odorant agents andsolubilizers.

The stabilizer(s), when they are present, preferably represent not morethan 5% by mass in the heat-transfer composition. Among the stabilizers,mention may be made especially of nitromethane, ascorbic acid,terephthalic acid, azoles such as tolutriazole or benzotriazole,phenolic compounds such as tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, epoxides (optionallyfluorinated or perfluorinated alkyl or alkenyl or aromatic) such asn-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidylether, butylphenylglycidyl ether, phosphites, phosphonates, thiols andlactones.

Lubricants that may especially be used include oils of mineral origin,silicone oils, paraffins of natural origin, naphthenes, syntheticparaffins, alkylbenzenes, poly-α-olefins, polyalkene glycols, polyolesters and/or polyvinyl ethers.

Nanoparticles that may especially be used include carbon nanoparticles,metal oxides (of copper or aluminum), TiO₂, Al₂O₃, MoS₂, etc.

As tracers (which can be detected), mention may be made of deuterated ornon-deuterated hydrofluorocarbons, deuterated hydrocarbons,perfluorocarbons, fluoroethers, brominated compounds, iodinatedcompounds, alcohols, aldehydes, ketones, nitrous oxide and combinationsthereof. The tracer is different from the heat-transfer compound(s) ofwhich the heat-transfer fluid is composed.

Solubilizers that may be mentioned include hydrocarbons, dimethyl ether,polyoxyalkylene ethers, amides, ketones, nitriles, chlorocarbons,esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes.The solubilizer is different from the heat-transfer compound(s) of whichthe heat-transfer fluid is composed.

Fluorescers that may be mentioned include naphthalimides, perylenes,coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes,naphthoxanthenes, fluoresceins and derivatives and combinations thereof.

Odorous agents that may be mentioned include alkyl acrylates, allylacrylates, acrylic acids, acryl esters, alkyl ethers, alkyl esters,alkynes, aldehydes, thiols, thioethers, disulfides, allylisothiocyanates, alkanoic acids, amines, norbornenes, norbornenederivatives, cyclohexene, heterocyclic aromatic compounds, ascaridole,o-methoxy(methyl)phenol and combinations thereof.

The heat-transfer process according to the invention is based on the useof an installation comprising a vapor compression circuit which containsa heat-transfer fluid. The heat-transfer process may be a process ofheating or cooling a fluid or a body.

The vapor compression circuit containing a heat-transfer fluid comprisesat least one evaporator, a compressor, a condenser and a depressurizer,and also lines for transporting heat-transfer fluid between theseelements. The evaporator and the condenser comprise a heat exchanger forexchanging heat between the heat-transfer fluid and another fluid orbody.

Compressors that may especially be used include a centrifugal compressorwith one or more stages or a mini centrifugal compressor. Rotary,spiral, piston or screw compressors may also be used. The compressor maybe driven by an electric motor or by a gas turbine (for example fed withthe exhaust gas from a vehicle, for mobile applications) or by gearing.

The installation may comprise a turbine for generating electricity(Rankine cycle).

The installation may optionally also comprise at least one heat-transferfluid used to transmit heat (with or without a change of state) betweenthe heat-transfer fluid circuit and the fluid or body to be heated orcooled.

The installation may also optionally comprise two (or more) vaporcompression circuits, containing identical or different heat-transferfluids. For example, the vapor compression circuits may be coupledtogether.

The vapor compression circuit functions according to a standard vaporcompression cycle. The cycle comprises the change of state of theheat-transfer fluid from a liquid phase (or liquid/vapor double phase)to a vapor phase at relatively low pressure, and then the compression ofthe fluid in the vapor phase up to a relatively high pressure, thechange of state (condensation) of the heat-transfer fluid from the vaporphase to the liquid phase at a relatively high pressure, and thereduction of the pressure to recommence the cycle.

In the case of a cooling process, heat derived from the fluid or bodythat is being cooled (directly or indirectly, via a heat-transfer fluid)is absorbed by the heat-transfer fluid, during its evaporation, and at arelatively low temperature relative to the environment. The coolingprocesses comprise air-conditioning (with mobile installations, forexample in vehicles, or stationary installations), refrigeration (withmobile installations, for example in containers, or stationaryinstallations) and freezing or cryogenic processes.

In the case of a heating process, heat is surrendered (directly orindirectly, via a heat-transfer fluid) from the heat-transfer fluid,during its condensation, to the fluid or body that is heated, at arelatively high temperature relative to the environment. Theinstallation for performing the heat transfer is referred to in thiscase as a “heat pump”.

It is possible to use any type of heat exchanger for the use of theheat-transfer fluids according to the invention, and especiallyco-current heat exchangers or, preferably, counter-current heatexchangers.

The heat-transfer fluids used in the context of the present inventionare compositions which comprise HFO-1336yf in combination with at leastone hydrocarbon, ether, hydrofluoroether, hydrofluorocarbon orfluoroolefin compound (preferably a hydrofluorocarbon, hydrocarbon orfluoroolefin compound) with a boiling point of less than or equal to−10° C. at a pressure of 101.325 kPa.

The boiling point may be measured according to standard NF EN 378-1 ofApril 2008.

Preferably, the compound is chosen from HFO-1234yf, HFO-1234ze,HFO-1234zc, HFO-1243zf, HFO-1243yf, HFC-134a, HFC-134, HFC-125,HFC-227ea, HFC-152a, HFC-263fb, HC-290 and HC-600a.

HFO-1234ze, HFO-1234yf, HFC-134a, HFC-134, HFC-263fb and HFC-152a arepreferred among these compounds.

The normal boiling points at 1 bar of these compounds are as follows, towithin 0.5° C.:

-   -   HFO-1234ze: −18.5° C.;    -   HFO-1234yf: −29.5° C.;    -   HFC-134a: −26° C.;    -   HFC-134: −17.5° C.;    -   HFC-263fb: −13.0° C.;    -   HFC-152a: −24.0° C.

In particular, the above compositions may be binary or ternary mixturesof compounds.

Binary mixtures are mixtures of two heat-transfer compounds. Ternarymixtures are mixtures of three heat-transfer compounds.

Impurities may or may not be present in such heat-transfer fluids. Whenthey are present, they represent less than 1%, preferably less than0.5%, preferably less than 0.1%, preferably less than 0.05% andpreferably less than 0.01% of the composition.

In the case of the ternary mixtures, the heat-transfer fluid maycomprise HFO-1336yf in combination with two compounds chosen fromHFO-1234yf, HFO-1234ze, HFO-1234zc, HFO-1243zf, HFO-1243yf, HFC-134a,HFC-134, HFC-125, HFC-227ea, HFC-152a, HFC-263fb HC-290 and HC-600a; oralternatively HFO-1336yf in combination with a compound chosen fromHFO-1234yf, HFO-1234ze, HFO-1234zc, HFO-1243zf, HFO-1243yf, HFC-134a,HFC-134, HFC-125, HFC-227ea, HFC-152a, HFC-263fb, HC-290 and HC-600a andalso an additional compound, preferably chosen from hydrocarbons,hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroethers, ethers(of hydrocarbons), fluoroolefins, ammonia and carbon dioxide.

In the above compositions, the HFO-1336yf may represent from 0.1% to 1%of the composition or from 1% to 2% of the composition; or from 2% to 3%of the composition; or from 3% to 4% of the composition; or from 4% to5% of the composition; or from 5% to 6% of the composition; or from 6%to 7% of the composition; or from 7% to 8% of the composition; or from8% to 9% of the composition; or from 9% to 10% of the composition; orfrom 10% to 11% of the composition; or from 11% to 12% of thecomposition; or from 12% to 13% of the composition; or from 13% to 14%of the composition; or from 14% to 15% of the composition; or from 15%to 16% of the composition; or from 16% to 17% of the composition; orfrom 17% to 18% of the composition; or from 18% to 19% of thecomposition; or from 19% to 20% of the composition; or from 20% to 21%of the composition; or from 21% to 22% of the composition; or from 22%to 23% of the composition; or from 23% to 24% of the composition; orfrom 24% to 25% of the composition; or from 25% to 26% of thecomposition; or from 26% to 27% of the composition; or from 27% to 28%of the composition; or from 28% to 29% of the composition; or from 29%to 30% of the composition; or from 30% to 31% of the composition; orfrom 31% to 32% of the composition; or from 32% to 33% of thecomposition; or from 33% to 34% of the composition; or from 34% to 35%of the composition; or from 35% to 36% of the composition; or from 36%to 37% of the composition; or from 37% to 38% of the composition; orfrom 38% to 39% of the composition; or from 39% to 40% of thecomposition; or from 40% to 41% of the composition; or from 41% to 42%of the composition; or from 42% to 43% of the composition; or from 43%to 44% of the composition; or from 44% to 45% of the composition; orfrom 45% to 46% of the composition; or from 46% to 47% of thecomposition; or from 47% to 48% of the composition; or from 48% to 49%of the composition; or from 49% to 50% of the composition; or from 50%to 51% of the composition; or from 51% to 52% of the composition; orfrom 52% to 53% of the composition; or from 53% to 54% of thecomposition; or from 54% to 55% of the composition; or from 55% to 56%of the composition; or from 56% to 57% of the composition; or from 57%to 58% of the composition; or from 58% to 59% of the composition; orfrom 59% to 60% of the composition; or from 60% to 61% of thecomposition; or from 61% to 62% of the composition; or from 62% to 63%of the composition; or from 63% to 64% of the composition; or from 64%to 65% of the composition; or from 65% to 66% of the composition; orfrom 66% to 67% of the composition; or from 67% to 68% of thecomposition; or from 68% to 69% of the composition; or from 69% to 70%of the composition; or from 70% to 71% of the composition; or from 71%to 72% of the composition; or from 72% to 73% of the composition; orfrom 73% to 74% of the composition; or from 74% to 75% of thecomposition; or from 75% to 76% of the composition; or from 76% to 77%of the composition; or from 77% to 78% of the composition; or from 78%to 79% of the composition; or from 79% to 80% of the composition; orfrom 80% to 81% of the composition; or from 81% to 82% of thecomposition; or from 82% to 83% of the composition; or from 83% to 84%of the composition; or from 84% to 85% of the composition; or from 85%to 86% of the composition; or from 86% to 87% of the composition; orfrom 87% to 88% of the composition; or from 88% to 89% of thecomposition; or from 89% to 90% of the composition; or from 90% to 91%of the composition; or from 91% to 92% of the composition; or from 92%to 93% of the composition; or from 93% to 94% of the composition; orfrom 94% to 95% of the composition; or from 95% to 96% of thecomposition; or from 96% to 97% of the composition; or from 97% to 98%of the composition; or from 98% to 99% of the composition; or from 99%to 99.9% of the composition. The content of HFO-1336yf may also varywithin several of the above intervals: for example from 1% to 2% andfrom 2% to 3%, i.e. starting from 1% to 3%, etc.

Furthermore, in the above compositions, the or each hydrocarbon, ether,hydrofluoroether, hydrofluorocarbon or fluoroolefin compound with aboiling point of less than or equal to −10° C. may represent from 0.1%to 1% of the composition; or from 1% to 2% of the composition; or from2% to 3% of the composition; or from 3% to 4% of the composition; orfrom 4% to 5% of the composition; or from 5% to 6% of the composition;or from 6% to 7% of the composition; or from 7% to 8% of thecomposition; or from 8% to 9% of the composition; or from 9% to 10% ofthe composition; or from 10% to 11% of the composition; or from 11% to12% of the composition; or from 12% to 13% of the composition; or from13% to 14% of the composition; or from 14% to 15% of the composition; orfrom 15% to 16% of the composition; or from 16% to 17% of thecomposition; or from 17% to 18% of the composition; or from 18% to 19%of the composition; or from 19% to 20% of the composition; or from 20%to 21% of the composition; or from 21% to 22% of the composition; orfrom 22% to 23% of the composition; or from 23% to 24% of thecomposition; or from 24% to 25% of the composition; or from 25% to 26%of the composition; or from 26% to 27% of the composition; or from 27%to 28% of the composition; or from 28% to 29% of the composition; orfrom 29% to 30% of the composition; or from 30% to 31% of thecomposition; or from 31% to 32% of the composition; or from 32% to 33%of the composition; or from 33% to 34% of the composition; or from 34%to 35% of the composition; or from 35% to 36% of the composition; orfrom 36% to 37% of the composition; or from 37% to 38% of thecomposition; or from 38% to 39% of the composition; or from 39% to 40%of the composition; or from 40% to 41% of the composition; or from 41%to 42% of the composition; or from 42% to 43% of the composition; orfrom 43% to 44% of the composition; or from 44% to 45% of thecomposition; or from 45% to 46% of the composition; or from 46% to 47%of the composition; or from 47% to 48% of the composition; or from 48%to 49% of the composition; or from 49% to 50% of the composition; orfrom 50% to 51% of the composition; or from 51% to 52% of thecomposition; or from 52% to 53% of the composition; or from 53% to 54%of the composition; or from 54% to 55% of the composition; or from 55%to 56% of the composition; or from 56% to 57% of the composition; orfrom 57% to 58% of the composition; or from 58% to 59% of thecomposition; or from 59% to 60% of the composition; or from 60% to 61%of the composition; or from 61% to 62% of the composition; or from 62%to 63% of the composition; or from 63% to 64% of the composition; orfrom 64% to 65% of the composition; or from 65% to 66% of thecomposition; or from 66% to 67% of the composition; or from 67% to 68%of the composition; or from 68% to 69% of the composition; or from 69%to 70% of the composition; or from 70% to 71% of the composition; orfrom 71% to 72% of the composition; or from 72% to 73% of thecomposition; or from 73% to 74% of the composition; or from 74% to 75%of the composition; or from 75% to 76% of the composition; or from 76%to 77% of the composition; or from 77% to 78% of the composition; orfrom 78% to 79% of the composition; or from 79% to 80% of thecomposition; or from 80% to 81% of the composition; or from 81% to 82%of the composition; or from 82% to 83% of the composition; or from 83%to 84% of the composition; or from 84% to 85% of the composition; orfrom 85% to 86% of the composition; or from 86% to 87% of thecomposition; or from 87% to 88% of the composition; or from 88% to 89%of the composition; or from 89% to 90% of the composition; or from 90%to 91% of the composition; or from 91% to 92% of the composition; orfrom 92% to 93% of the composition; or from 93% to 94% of thecomposition; or from 94% to 95% of the composition; or from 95% to 96%of the composition; or from 96% to 97% of the composition; or from 97%to 98% of the composition; or from 98% to 99% of the composition; orfrom 99% to 99.9% of the composition. The content of the compound or ofeach compound may also vary within several of the above intervals: forexample from 1% to 2% and from 2% to 3%, i.e. from 1% to 3%, etc.

Preferred compositions are:

-   -   the binary mixture of HFO-1336yf and HFO-1234ze (and especially        HFO-E-1234ze);    -   the binary mixture of HFO-1336yf and HFC-263fb;    -   the binary mixture of HFO-1336yf and HFC-134;    -   the binary mixture of HFO-1336yf and HFC-134a;    -   the binary mixture of HFO-1336yf and HFC-152a;    -   the ternary mixture of HFO-1336yf, de HFC-134a and HFO-1234ze        (especially HFO-E-1234ze);    -   the ternary mixture of HFO-1336yf, de HFC-134a and HFC-263fb;    -   the ternary mixture of HFO-1336yf, de HFC-134a and HFC-152a;    -   the ternary mixture of HFO-1336yf, de HFC-134 and HFO-1234ze        (especially HFO-E-1234ze); et    -   the ternary mixture of HFO-1336yf, de HFC-134 and HFC-263fb.

In certain embodiments, the composition according to the invention hasone of the formulations listed in the table below:

HFO-1336yf HFO-1234ze Composition 1 from 1% to 5% from 95% to 99%Composition 2 from 5% to 10% from 90% to 95% Composition 3 from 10% to15% from 85% to 90% Composition 4 from 15% to 20% from 80% to 85%Composition 5 from 20% to 25% from 75% to 80% Composition 6 from 25% to30% from 70% to 75% Composition 7 from 30% to 35% from 65% to 70%Composition 8 from 35% to 40% from 60% to 65% Composition 9 from 40% to45% from 55% to 60% Composition 10 from 45% to 50% from 50% to 55%Composition 11 from 50% to 55% from 45% to 50% Composition 12 from 55%to 60% from 40% to 45% Composition 13 from 60% to 65% from 35% to 40%Composition 14 from 65% to 70% from 30% to 35% Composition 15 from 70%to 75% from 25% to 30% Composition 16 from 75% to 80% from 20% to 25%Composition 17 from 80% to 85% from 15% to 20% Composition 18 from 85%to 90% from 10% to 15% Composition 19 from 90% to 95% from 5% to 10%Composition 20 from 95% to 99% from 1% to 5%

In certain embodiments, the composition according to the invention hasone of the formulations listed in the table below:

HFO-1336yf HFC-263fb Composition 1 from 1% to 5% from 95% to 99%Composition 2 from 5% to 10% from 90% to 95% Composition 3 from 10% to15% from 85% to 90% Composition 4 from 15% to 20% from 80% to 85%Composition 5 from 20% to 25% from 75% to 80% Composition 6 from 25% to30% from 70% to 75% Composition 7 from 30% to 35% from 65% to 70%Composition 8 from 35% to 40% from 60% to 65% Composition 9 from 40% to45% from 55% to 60% Composition 10 from 45% to 50% from 50% to 55%Composition 11 from 50% to 55% from 45% to 50% Composition 12 from 55%to 60% from 40% to 45% Composition 13 from 60% to 65% from 35% to 40%Composition 14 from 65% to 70% from 30% to 35% Composition 15 from 70%to 75% from 25% to 30% Composition 16 from 75% to 80% from 20% to 25%Composition 17 from 80% to 85% from 15% to 20% Composition 18 from 85%to 90% from 10% to 15% Composition 19 from 90% to 95% from 5% to 10%Composition 20 from 95% to 99% from 1% to 5%

In certain embodiments, the composition according to the invention hasone of the formulations listed in the table below:

HFO-1336yf HFC-134 Composition 1 from 1% to 5% from 95% to 99%Composition 2 from 5% to 10% from 90% to 95% Composition 3 from 10% to15% from 85% to 90% Composition 4 from 15% to 20% from 80% to 85%Composition 5 from 20% to 25% from 75% to 80% Composition 6 from 25% to30% from 70% to 75% Composition 7 from 30% to 35% from 65% to 70%Composition 8 from 35% to 40% from 60% to 65% Composition 9 from 40% to45% from 55% to 60% Composition 10 from 45% to 50% from 50% to 55%Composition 11 from 50% to 55% from 45% to 50% Composition 12 from 55%to 60% from 40% to 45% Composition 13 from 60% to 65% from 35% to 40%Composition 14 from 65% to 70% from 30% to 35% Composition 15 from 70%to 75% from 25% to 30% Composition 16 from 75% to 80% from 20% to 25%Composition 17 from 80% to 85% from 15% to 20% Composition 18 from 85%to 90% from 10% to 15% Composition 19 from 90% to 95% from 5% to 10%Composition 20 from 95% to 99% from 1% to 5%

In certain embodiments, the composition according to the invention hasone of the formulations listed in the table below:

HFO-1336yf HFC-134a Composition 1 from 1% to 5% from 95% to 99%Composition 2 from 5% to 10% from 90% to 95% Composition 3 from 10% to15% from 85% to 90% Composition 4 from 15% to 20% from 80% to 85%Composition 5 from 20% to 25% from 75% to 80% Composition 6 from 25% to30% from 70% to 75% Composition 7 from 30% to 35% from 65% to 70%Composition 8 from 35% to 40% from 60% to 65% Composition 9 from 40% to45% from 55% to 60% Composition 10 from 45% to 50% from 50% to 55%Composition 11 from 50% to 55% from 45% to 50% Composition 12 from 55%to 60% from 40% to 45% Composition 13 from 60% to 65% from 35% to 40%Composition 14 from 65% to 70% from 30% to 35% Composition 15 from 70%to 75% from 25% to 30% Composition 16 from 75% to 80% from 20% to 25%Composition 17 from 80% to 85% from 15% to 20% Composition 18 from 85%to 90% from 10% to 15% Composition 19 from 90% to 95% from 5% to 10%Composition 20 from 95% to 99% from 1% to 5%

In certain embodiments, the composition according to the invention hasone of the formulations listed in the table below:

HFO-1336yf HFC-152a Composition 1 from 1% to 5% from 95% to 99%Composition 2 from 5% to 10% from 90% to 95% Composition 3 from 10% to15% from 85% to 90% Composition 4 from 15% to 20% from 80% to 85%Composition 5 from 20% to 25% from 75% to 80% Composition 6 from 25% to30% from 70% to 75% Composition 7 from 30% to 35% from 65% to 70%Composition 8 from 35% to 40% from 60% to 65% Composition 9 from 40% to45% from 55% to 60% Composition 10 from 45% to 50% from 50% to 55%Composition 11 from 50% to 55% from 45% to 50% Composition 12 from 55%to 60% from 40% to 45% Composition 13 from 60% to 65% from 35% to 40%Composition 14 from 65% to 70% from 30% to 35% Composition 15 from 70%to 75% from 25% to 30% Composition 16 from 75% to 80% from 20% to 25%Composition 17 from 80% to 85% from 15% to 20% Composition 18 from 85%to 90% from 10% to 15% Composition 19 from 90% to 95% from 5% to 10%Composition 20 from 95% to 99% from 1% to 5%

In certain embodiments, the composition according to the invention hasone of the formulations listed in the table below:

HFO-1336yf HFC-134a HFO-1234ze Composition 1 from 1% to 10% from 1% to10% from 80% to 98% Composition 2 from 1% to 10% from 10% to 20% from70% to 89% Composition 3 from 1% to 10% from 20% to 30% from 60% to 79%Composition 4 from 1% to 10% from 30% to 40% from 50% to 69% Composition5 from 1% to 10% from 40% to 50% from 40% to 59% Composition 6 from 1%to 10% from 50% to 60% from 30% to 49% Composition 7 from 1% to 10% from60% to 70% from 20% to 39% Composition 8 from 1% to 10% from 70% to 80%from 10% to 29% Composition 9 from 1% to 10% from 80% to 90% from 1% to19% Composition 10 from 1% to 10% from 90% to 98% from 1% to 9%Composition 11 from 10% to 20% from 1% to 10% from 70% to 89%Composition 12 from 10% to 20% from 10% to 20% from 60% to 80%Composition 13 from 10% to 20% from 20% to 30% from 50% to 70%Composition 14 from 10% to 20% from 30% to 40% from 40% to 60%Composition 15 from 10% to 20% from 40% to 50% from 30% to 50%Composition 16 from 10% to 20% from 50% to 60% from 20% to 40%Composition 17 from 10% to 20% from 60% to 70% from 10% to 30%Composition 18 from 10% to 20% from 70% to 80% from 1% to 20%Composition 19 from 10% to 20% from 80% to 90% from 1% to 10%Composition 20 from 20% to 30% from 1% to 10% from 60% to 79%Composition 21 from 20% to 30% from 10% to 20% from 50% to 70%Composition 22 from 20% to 30% from 20% to 30% from 40% to 60%Composition 23 from 20% to 30% from 30% to 40% from 30% to 50%Composition 24 from 20% to 30% from 40% to 50% from 20% to 40%Composition 25 from 20% to 30% from 50% to 60% from 10% to 30%Composition 26 from 20% to 30% from 60% to 70% from 1% to 20%Composition 27 from 20% to 30% from 70% to 80% from 1% to 10%Composition 28 from 30% to 40% from 1% to 10% from 50% to 69%Composition 29 from 30% to 40% from 10% to 20% from 40% to 60%Composition 30 from 30% to 40% from 20% to 30% from 30% to 50%Composition 31 from 30% to 40% from 30% to 40% from 20% to 40%Composition 32 from 30% to 40% from 40% to 50% from 10% to 30%Composition 33 from 30% to 40% from 50% to 60% from 1% to 20%Composition 34 from 30% to 40% from 60% to 70% from 1% to 10%Composition 35 from 40% to 50% from 1% to 10% from 40% to 59%Composition 36 from 40% to 50% from 10% to 20% from 30% to 50%Composition 37 from 40% to 50% from 20% to 30% from 20% to 40%Composition 38 from 40% to 50% from 30% to 40% from 10% to 30%Composition 39 from 40% to 50% from 40% to 50% from 1% to 20%Composition 40 from 40% to 50% from 50% to 60% from 1% to 10%Composition 41 from 50% to 60% from 1% to 10% from 30% to 49%Composition 42 from 50% to 60% from 10% to 20% from 20% to 40%Composition 43 from 50% to 60% from 20% to 30% from 10% to 30%Composition 44 from 50% to 60% from 30% to 40% from 1% to 20%Composition 45 from 50% to 60% from 40% to 50% from 1% to 10%Composition 46 from 60% to 70% from 1% to 10% from 20% to 39%Composition 47 from 60% to 70% from 10% to 20% from 10% to 30%Composition 48 from 60% to 70% from 20% to 30% from 1% to 20%Composition 49 from 60% to 70% from 30% to 40% from 1% to 10%Composition 50 from 70% to 80% from 1% to 10% from 10% to 29%Composition 51 from 70% to 80% from 10% to 20% from 1% to 20%Composition 52 from 70% to 80% from 20% to 30% from 1% to 10%Composition 53 from 80% to 90% from 1% to 10% from 1% to 19% Composition54 from 80% to 90% from 10% to 20% from 1% to 10% Composition 55 from90% to 98% from 1% to 9% from 1% to 9%

In certain embodiments, the composition according to the invention hasone of the formulations listed in the table below:

HFO-1336yf HFC-134a HFC-263fb Composition 1 from 1% to 10% from 1% to10% from 80% to 98% Composition 2 from 1% to 10% from 10% to 20% from70% to 89% Composition 3 from 1% to 10% from 20% to 30% from 60% to 79%Composition 4 from 1% to 10% from 30% to 40% from 50% to 69% Composition5 from 1% to 10% from 40% to 50% from 40% to 59% Composition 6 from 1%to 10% from 50% to 60% from 30% to 49% Composition 7 from 1% to 10% from60% to 70% from 20% to 39% Composition 8 from 1% to 10% from 70% to 80%from 10% to 29% Composition 9 from 1% to 10% from 80% to 90% from 1% to19% Composition 10 from 1% to 10% from 90% to 98% from 1% to 9%Composition 11 from 10% to 20% from 1% to 10% from 70% to 89%Composition 12 from 10% to 20% from 10% to 20% from 60% to 80%Composition 13 from 10% to 20% from 20% to 30% from 50% to 70%Composition 14 from 10% to 20% from 30% to 40% from 40% to 60%Composition 15 from 10% to 20% from 40% to 50% from 30% to 50%Composition 16 from 10% to 20% from 50% to 60% from 20% to 40%Composition 17 from 10% to 20% from 60% to 70% from 10% to 30%Composition 18 from 10% to 20% from 70% to 80% from 1% to 20%Composition 19 from 10% to 20% from 80% to 90% from 1% to 10%Composition 20 from 20% to 30% from 1% to 10% from 60% to 79%Composition 21 from 20% to 30% from 10% to 20% from 50% to 70%Composition 22 from 20% to 30% from 20% to 30% from 40% to 60%Composition 23 from 20% to 30% from 30% to 40% from 30% to 50%Composition 24 from 20% to 30% from 40% to 50% from 20% to 40%Composition 25 from 20% to 30% from 50% to 60% from 10% to 30%Composition 26 from 20% to 30% from 60% to 70% from 1% to 20%Composition 27 from 20% to 30% from 70% to 80% from 1% to 10%Composition 28 from 30% to 40% from 1% to 10% from 50% to 69%Composition 29 from 30% to 40% from 10% to 20% from 40% to 60%Composition 30 from 30% to 40% from 20% to 30% from 30% to 50%Composition 31 from 30% to 40% from 30% to 40% from 20% to 40%Composition 32 from 30% to 40% from 40% to 50% from 10% to 30%Composition 33 from 30% to 40% from 50% to 60% from 1% to 20%Composition 34 from 30% to 40% from 60% to 70% from 1% to 10%Composition 35 from 40% to 50% from 1% to 10% from 40% to 59%Composition 36 from 40% to 50% from 10% to 20% from 30% to 50%Composition 37 from 40% to 50% from 20% to 30% from 20% to 40%Composition 38 from 40% to 50% from 30% to 40% from 10% to 30%Composition 39 from 40% to 50% from 40% to 50% from 1% to 20%Composition 40 from 40% to 50% from 50% to 60% from 1% to 10%Composition 41 from 50% to 60% from 1% to 10% from 30% to 49%Composition 42 from 50% to 60% from 10% to 20% from 20% to 40%Composition 43 from 50% to 60% from 20% to 30% from 10% to 30%Composition 44 from 50% to 60% from 30% to 40% from 1% to 20%Composition 45 from 50% to 60% from 40% to 50% from 1% to 10%Composition 46 from 60% to 70% from 1% to 10% from 20% to 39%Composition 47 from 60% to 70% from 10% to 20% from 10% to 30%Composition 48 from 60% to 70% from 20% to 30% from 1% to 20%Composition 49 from 60% to 70% from 30% to 40% from 1% to 10%Composition 50 from 70% to 80% from 1% to 10% from 10% to 29%Composition 51 from 70% to 80% from 10% to 20% from 1% to 20%Composition 52 from 70% to 80% from 20% to 30% from 1% to 10%Composition 53 from 80% to 90% from 1% to 10% from 1% to 19% Composition54 from 80% to 90% from 10% to 20% from 1% to 10% Composition 55 from90% to 98% from 1% to 9% from 1% to 9%

In certain embodiments, the composition according to the invention hasone of the formulations listed in the table below:

HFO-1336yf HFC-134a HFC-152a Composition 1 from 1% to 10% from 1% to 10%from 80% to 98% Composition 2 from 1% to 10% from 10% to 20% from 70% to89% Composition 3 from 1% to 10% from 20% to 30% from 60% to 79%Composition 4 from 1% to 10% from 30% to 40% from 50% to 69% Composition5 from 1% to 10% from 40% to 50% from 40% to 59% Composition 6 from 1%to 10% from 50% to 60% from 30% to 49% Composition 7 from 1% to 10% from60% to 70% from 20% to 39% Composition 8 from 1% to 10% from 70% to 80%from 10% to 29% Composition 9 from 1% to 10% from 80% to 90% from 1% to19% Composition 10 from 1% to 10% from 90% to 98% from 1% to 9%Composition 11 from 10% to 20% from 1% to 10% from 70% to 89%Composition 12 from 10% to 20% from 10% to 20% from 60% to 80%Composition 13 from 10% to 20% from 20% to 30% from 50% to 70%Composition 14 from 10% to 20% from 30% to 40% from 40% to 60%Composition 15 from 10% to 20% from 40% to 50% from 30% to 50%Composition 16 from 10% to 20% from 50% to 60% from 20% to 40%Composition 17 from 10% to 20% from 60% to 70% from 10% to 30%Composition 18 from 10% to 20% from 70% to 80% from 1% to 20%Composition 19 from 10% to 20% from 80% to 90% from 1% to 10%Composition 20 from 20% to 30% from 1% to 10% from 60% to 79%Composition 21 from 20% to 30% from 10% to 20% from 50% to 70%Composition 22 from 20% to 30% from 20% to 30% from 40% to 60%Composition 23 from 20% to 30% from 30% to 40% from 30% to 50%Composition 24 from 20% to 30% from 40% to 50% from 20% to 40%Composition 25 from 20% to 30% from 50% to 60% from 10% to 30%Composition 26 from 20% to 30% from 60% to 70% from 1% to 20%Composition 27 from 20% to 30% from 70% to 80% from 1% to 10%Composition 28 from 30% to 40% from 1% to 10% from 50% to 69%Composition 29 from 30% to 40% from 10% to 20% from 40% to 60%Composition 30 from 30% to 40% from 20% to 30% from 30% to 50%Composition 31 from 30% to 40% from 30% to 40% from 20% to 40%Composition 32 from 30% to 40% from 40% to 50% from 10% to 30%Composition 33 from 30% to 40% from 50% to 60% from 1% to 20%Composition 34 from 30% to 40% from 60% to 70% from 1% to 10%Composition 35 from 40% to 50% from 1% to 10% from 40% to 59%Composition 36 from 40% to 50% from 10% to 20% from 30% to 50%Composition 37 from 40% to 50% from 20% to 30% from 20% to 40%Composition 38 from 40% to 50% from 30% to 40% from 10% to 30%Composition 39 from 40% to 50% from 40% to 50% from 1% to 20%Composition 40 from 40% to 50% from 50% to 60% from 1% to 10%Composition 41 from 50% to 60% from 1% to 10% from 30% to 49%Composition 42 from 50% to 60% from 10% to 20% from 20% to 40%Composition 43 from 50% to 60% from 20% to 30% from 10% to 30%Composition 44 from 50% to 60% from 30% to 40% from 1% to 20%Composition 45 from 50% to 60% from 40% to 50% from 1% to 10%Composition 46 from 60% to 70% from 1% to 10% from 20% to 39%Composition 47 from 60% to 70% from 10% to 20% from 10% to 30%Composition 48 from 60% to 70% from 20% to 30% from 1% to 20%Composition 49 from 60% to 70% from 30% to 40% from 1% to 10%Composition 50 from 70% to 80% from 1% to 10% from 10% to 29%Composition 51 from 70% to 80% from 10% to 20% from 1% to 20%Composition 52 from 70% to 80% from 20% to 30% from 1% to 10%Composition 53 from 80% to 90% from 1% to 10% from 1% to 19% Composition54 from 80% to 90% from 10% to 20% from 1% to 10% Composition 55 from90% to 98% from 1% to 9% from 1% to 9%

In certain embodiments, the composition according to the invention hasone of the formulations listed in the table below:

HFO-1336yf HFC-134 HFO-1234ze Composition 1 from 1% to 10% from 1% to10% from 80% to 98% Composition 2 from 1% to 10% from 10% to 20% from70% to 89% Composition 3 from 1% to 10% from 20% to 30% from 60% to 79%Composition 4 from 1% to 10% from 30% to 40% from 50% to 69% Composition5 from 1% to 10% from 40% to 50% from 40% to 59% Composition 6 from 1%to 10% from 50% to 60% from 30% to 49% Composition 7 from 1% to 10% from60% to 70% from 20% to 39% Composition 8 from 1% to 10% from 70% to 80%from 10% to 29% Composition 9 from 1% to 10% from 80% to 90% from 1% to19% Composition 10 from 1% to 10% from 90% to 98% from 1% to 9%Composition 11 from 10% to 20% from 1% to 10% from 70% to 89%Composition 12 from 10% to 20% from 10% to 20% from 60% to 80%Composition 13 from 10% to 20% from 20% to 30% from 50% to 70%Composition 14 from 10% to 20% from 30% to 40% from 40% to 60%Composition 15 from 10% to 20% from 40% to 50% from 30% to 50%Composition 16 from 10% to 20% from 50% to 60% from 20% to 40%Composition 17 from 10% to 20% from 60% to 70% from 10% to 30%Composition 18 from 10% to 20% from 70% to 80% from 1% to 20%Composition 19 from 10% to 20% from 80% to 90% from 1% to 10%Composition 20 from 20% to 30% from 1% to 10% from 60% to 79%Composition 21 from 20% to 30% from 10% to 20% from 50% to 70%Composition 22 from 20% to 30% from 20% to 30% from 40% to 60%Composition 23 from 20% to 30% from 30% to 40% from 30% to 50%Composition 24 from 20% to 30% from 40% to 50% from 20% to 40%Composition 25 from 20% to 30% from 50% to 60% from 10% to 30%Composition 26 from 20% to 30% from 60% to 70% from 1% to 20%Composition 27 from 20% to 30% from 70% to 80% from 1% to 10%Composition 28 from 30% to 40% from 1% to 10% from 50% to 69%Composition 29 from 30% to 40% from 10% to 20% from 40% to 60%Composition 30 from 30% to 40% from 20% to 30% from 30% to 50%Composition 31 from 30% to 40% from 30% to 40% from 20% to 40%Composition 32 from 30% to 40% from 40% to 50% from 10% to 30%Composition 33 from 30% to 40% from 50% to 60% from 1% to 20%Composition 34 from 30% to 40% from 60% to 70% from 1% to 10%Composition 35 from 40% to 50% from 1% to 10% from 40% to 59%Composition 36 from 40% to 50% from 10% to 20% from 30% to 50%Composition 37 from 40% to 50% from 20% to 30% from 20% to 40%Composition 38 from 40% to 50% from 30% to 40% from 10% to 30%Composition 39 from 40% to 50% from 40% to 50% from 1% to 20%Composition 40 from 40% to 50% from 50% to 60% from 1% to 10%Composition 41 from 50% to 60% from 1% to 10% from 30% to 49%Composition 42 from 50% to 60% from 10% to 20% from 20% to 40%Composition 43 from 50% to 60% from 20% to 30% from 10% to 30%Composition 44 from 50% to 60% from 30% to 40% from 1% to 20%Composition 45 from 50% to 60% from 40% to 50% from 1% to 10%Composition 46 from 60% to 70% from 1% to 10% from 20% to 39%Composition 47 from 60% to 70% from 10% to 20% from 10% to 30%Composition 48 from 60% to 70% from 20% to 30% from 1% to 20%Composition 49 from 60% to 70% from 30% to 40% from 1% to 10%Composition 50 from 70% to 80% from 1% to 10% from 10% to 29%Composition 51 from 70% to 80% from 10% to 20% from 1% to 20%Composition 52 from 70% to 80% from 20% to 30% from 1% to 10%Composition 53 from 80% to 90% from 1% to 10% from 1% to 19% Composition54 from 80% to 90% from 10% to 20% from 1% to 10% Composition 55 from90% to 98% from 1% to 9% from 1% to 9%

In certain embodiments, the composition according to the invention hasone of the formulations listed in the table below:

HFO-1336yf HFC-134 HFC-263fb Composition 1 from 1% to 10% from 1% to 10%from 80% to 98% Composition 2 from 1% to 10% from 10% to 20% from 70% to89% Composition 3 from 1% to 10% from 20% to 30% from 60% to 79%Composition 4 from 1% to 10% from 30% to 40% from 50% to 69% Composition5 from 1% to 10% from 40% to 50% from 40% to 59% Composition 6 from 1%to 10% from 50% to 60% from 30% to 49% Composition 7 from 1% to 10% from60% to 70% from 20% to 39% Composition 8 from 1% to 10% from 70% to 80%from 10% to 29% Composition 9 from 1% to 10% from 80% to 90% from 1% to19% Composition 10 from 1% to 10% from 90% to 98% from 1% to 9%Composition 11 from 10% to 20% from 1% to 10% from 70% to 89%Composition 12 from 10% to 20% from 10% to 20% from 60% to 80%Composition 13 from 10% to 20% from 20% to 30% from 50% to 70%Composition 14 from 10% to 20% from 30% to 40% from 40% to 60%Composition 15 from 10% to 20% from 40% to 50% from 30% to 50%Composition 16 from 10% to 20% from 50% to 60% from 20% to 40%Composition 17 from 10% to 20% from 60% to 70% from 10% to 30%Composition 18 from 10% to 20% from 70% to 80% from 1% to 20%Composition 19 from 10% to 20% from 80% to 90% from 1% to 10%Composition 20 from 20% to 30% from 1% to 10% from 60% to 79%Composition 21 from 20% to 30% from 10% to 20% from 50% to 70%Composition 22 from 20% to 30% from 20% to 30% from 40% to 60%Composition 23 from 20% to 30% from 30% to 40% from 30% to 50%Composition 24 from 20% to 30% from 40% to 50% from 20% to 40%Composition 25 from 20% to 30% from 50% to 60% from 10% to 30%Composition 26 from 20% to 30% from 60% to 70% from 1% to 20%Composition 27 from 20% to 30% from 70% to 80% from 1% to 10%Composition 28 from 30% to 40% from 1% to 10% from 50% to 69%Composition 29 from 30% to 40% from 10% to 20% from 40% to 60%Composition 30 from 30% to 40% from 20% to 30% from 30% to 50%Composition 31 from 30% to 40% from 30% to 40% from 20% to 40%Composition 32 from 30% to 40% from 40% to 50% from 10% to 30%Composition 33 from 30% to 40% from 50% to 60% from 1% to 20%Composition 34 from 30% to 40% from 60% to 70% from 1% to 10%Composition 35 from 40% to 50% from 1% to 10% from 40% to 59%Composition 36 from 40% to 50% from 10% to 20% from 30% to 50%Composition 37 from 40% to 50% from 20% to 30% from 20% to 40%Composition 38 from 40% to 50% from 30% to 40% from 10% to 30%Composition 39 from 40% to 50% from 40% to 50% from 1% to 20%Composition 40 from 40% to 50% from 50% to 60% from 1% to 10%Composition 41 from 50% to 60% from 1% to 10% from 30% to 49%Composition 42 from 50% to 60% from 10% to 20% from 20% to 40%Composition 43 from 50% to 60% from 20% to 30% from 10% to 30%Composition 44 from 50% to 60% from 30% to 40% from 1% to 20%Composition 45 from 50% to 60% from 40% to 50% from 1% to 10%Composition 46 from 60% to 70% from 1% to 10% from 20% to 39%Composition 47 from 60% to 70% from 10% to 20% from 10% to 30%Composition 48 from 60% to 70% from 20% to 30% from 1% to 20%Composition 49 from 60% to 70% from 30% to 40% from 1% to 10%Composition 50 from 70% to 80% from 1% to 10% from 10% to 29%Composition 51 from 70% to 80% from 10% to 20% from 1% to 20%Composition 52 from 70% to 80% from 20% to 30% from 1% to 10%Composition 53 from 80% to 90% from 1% to 10% from 1% to 19% Composition54 from 80% to 90% from 10% to 20% from 1% to 10% Composition 55 from90% to 98% from 1% to 9% from 1% to 9%

Among the above compositions, some of them have the advantage of beingquasi-azeotropic.

The term “quasi-azeotropic” denotes compositions for which, at constanttemperature, the liquid saturation pressure and the vapor saturationpressure are virtually identical (the maximum pressure difference being10%, or even advantageously 5%, relative to the liquid saturationpressure). These heat-transfer fluids have an advantage of ease of use.In the absence of a significant temperature glide, there is nosignificant change in the circulating composition, nor any significantchange in the composition in the case of leakage.

Some of the compositions of the invention are quasi-azeotropic at areference temperature of −5° C.

Some of the compositions of the invention are inflammable, within themeaning of standard ASHRAE 34-2007, and preferably with a testtemperature of 60° C. instead of 100° C.

Some of the compositions of the invention have performance qualitiesthat are equivalent and/or improved relative to a referenceheat-transfer fluid, for example HFO-1234ze or HC-600a.

These performance qualities may especially be the volumetric capacityand/or the coefficient of performance.

The equivalent or improved performance qualities may especially bechecked for the moderate-temperature cooling processes, i.e. those inwhich the temperature of the cooled fluid or body is from −15° C. to 15°C., preferably from −10° C. to 10° C. and more particularly preferablyfrom −5° C. to 5° C. (ideally about 0° C.).

The equivalent or improved performance qualities may alternatively bechecked for moderate-temperature heating processes, i.e. those in whichthe temperature of the heated fluid or body is from 30° C. to 80° C.,preferably from 35° C. to 55° C. and more particularly preferably from40° C. to 50° C. (ideally about 45° C.).

In the “moderate-temperature cooling or heating” processes mentionedabove, the inlet temperature of the heat-transfer fluid to theevaporator is preferably from −20° C. to 10° C., especially from −15° C.to 5° C. and more particularly preferably from −10° C. to 0° C., forexample about −5° C.; and the condensation-start temperature of theheat-transfer fluid in the condenser is preferably from 25° C. to 90°C., especially from 30° C. to 70° C. and more particularly preferablyfrom 35° C. to 55° C., for example about 50° C. These processes may berefrigeration, air-conditioning or heating processes.

The equivalent or improved performance qualities may alternatively bechecked for low-temperature refrigeration processes, i.e. those in whichthe temperature of the cooled fluid or body is from −40° C. to −10° C.,preferably from −35° C. to −25° C. and more particularly preferably from−30° C. to −20° C. (ideally about −25° C.).

In the “low-temperature refrigeration” processes mentioned above, theinlet temperature of the heat-transfer fluid to the evaporator ispreferably from −45° C. to −15° C., especially from −40° C. to −20° C.and more particularly preferably from −35° C. to −25° C., for exampleabout −30° C.; and the condensation-start temperature of theheat-transfer fluid in the condenser is preferably from 25° C. to 80°C., especially from 30° C. to 60° C. and more particularly preferablyfrom 35° C. to 55° C., for example about 40° C.

Some compositions of the invention are also particularly advantageousfor high-temperature heating processes, i.e. those in which thetemperature of the heated fluid or body is greater than 90° C., forexample greater than or equal to 110° C. or greater than or equal to130° C., and preferably less than or equal to 170° C.

Some compositions of the invention are also particularly advantageousfor refrigerated transportation applications and especially refrigeratedcontainers.

The compositions according to the invention may serve to replace variousheat-transfer fluids in various heat-transfer applications. For example,the compositions according to the invention may serve to replace:

-   -   1,1,1,2-tetrafluoroethane (R134a);    -   1,1-difluoroethane (R152a);    -   1,1,1,3,3-pentafluoropropane (R245fa);    -   mixtures of pentafluoroethane (R125), 1,1,1,2-tetrafluoroethane        (R134a) and isobutane (R600a), namely R422;    -   chlorodifluoromethane (R22);    -   the mixture of 51.2% chloropentafluoroethane (R115) and 48.8%        chlorodifluoromethane (R22), namely R502;    -   any hydrocarbon;    -   the mixture of 20% difluoromethane (R32), 40% pentafluoroethane        (R125) and 40% 1,1,1,2-tetrafluoroethane (R134a), namely R407A;    -   the mixture of 23% difluoromethane (R32), 25% pentafluoroethane        (R125) and 52% 1,1,1,2-tetrafluoroethane (R134a), namely R407C;    -   the mixture of 30% difluoromethane (R32), 30% pentafluoroethane        (R125) and 40% 1,1,1,2-tetrafluoroethane (R134a), namely R407F;    -   the mixture of 44% pentafluoroethane (R125), 52%        1,1,1-trifluoroethane (R143a) and 4% 1,1,1,2-tetrafluoroethane        (R134a), namely R404A;    -   R1234yf (2,3,3,3-tetrafluoropropene);    -   R1234ze (1,3,3,3-tetrafluoropropene).

The compositions according to the invention may also be useful asexpansion agents, propellants (for example for an aerosol), cleaningagents or solvents, besides their use as heat-transfer fluids.

As propellants, the compositions according to the invention may be usedalone or in combination with known propellants. The propellantcomprises, and preferably consists of, a composition according to theinvention. The active substance that is to be sprayed may be mixed withthe propellant and inert compounds, solvents or other additives, to forma composition to be sprayed. Preferably, the composition to be sprayedis an aerosol.

As expansion agent, the compositions according to the invention may beincluded in an expansion composition, which preferably comprises one ormore other compounds that are capable of reacting and of forming a foamor cellular structure under suitable conditions, as is known to thoseskilled in the art.

In particular, the invention proposes a process for preparing anexpanded thermoplastic product, first comprising the preparation of apolymeric expansion composition. Typically, the polymeric expansioncomposition is prepared by plasticizing a polymeric resin and by mixingthe compounds of an expansion agent composition at an initial pressure.The plasticization of the polymer resin may be performed under theeffect of heat, by heating the polymer resin to soften it sufficientlyto mix an expansion agent composition. Generally, the plasticizationtemperature is close to the glass transition temperature or the meltingpoint for crystalline polymers.

Other uses of the compositions according to the invention comprise usesas solvents, cleaning agents or the like. Examples that may be mentionedinclude steam degreasing, precision cleaning, the cleaning of electroniccircuits, dry cleaning, abrasive cleaning, solvents for depositinglubricants and release agents, and other solvent or surface treatments.

Example 1—Method for Calculating the Properties of the Heat-TransferFluids in the Various Configurations Envisaged

The RK-Soave equation is used for calculating the densities, enthalpies,entropies and liquid/vapor equilibrium data for the mixtures. The use ofthis equation requires knowledge of the properties of the puresubstances used in the mixtures under consideration and also thecoefficients of interaction for each binary mixture.

The data available for each pure substance are the boiling point, thecritical temperature and the critical pressure, the pressure curve as afunction of the temperature from the boiling point up to the criticalpoint, the saturated liquid density and saturated vapor density as afunction of the temperature.

The data regarding HFCs are published in the ASHRAE Handbook 2005,chapter 20, and are also available under Refrop (software developed byNIST for calculating the properties of cold-generating fluids).

The data of the temperature-pressure curve for HFOs are measured via thestatic method. The critical temperature and the critical pressure aremeasured with a C80 calorimeter sold by Setaram.

The RK-Soave equation uses coefficients of binary interaction torepresent the behavior of the products as mixtures. The coefficients arecalculated as a function of the experimental liquid/vapor equilibriumdata.

The technique used for the liquid/vapor equilibrium measurements is thestatic analytical cell method. The equilibrium cell comprises a sapphiretube and is equipped with two electromagnetic ROLSITM samplers. It isimmersed in a cryothermostatic bath (Huber HS40). A field-drivenmagnetic stirrer rotating at variable speed is used to accelerate theestablishment of the equilibria. The samples are analyzed by gaschromatography (HP5890 series II) using a catharometer (TCD).

The liquid/vapor equilibrium measurements on the HFC-134/HFO-1234zebinary mixture are performed on the following isotherm: 20° C.

The liquid/vapor equilibrium measurements on the HFC-134/HFC-263fbbinary mixture are performed on the following isotherm: 30° C.

The liquid/vapor equilibrium measurements on the HFC-134/HFO-1336yfbinary mixture are performed for the following isotherm: 50° C.

The liquid/vapor equilibrium measurements on the HFC-134a/HFO-1234zebinary mixture are performed for the following isotherm: 20° C.

The liquid/vapor equilibrium measurements on the HFC-134a/HFC-263fbbinary mixture are performed for the following isotherm: 30° C.

The liquid/vapor equilibrium measurements on the HFC-134a/HFO-1336yfbinary mixture are performed for the following isotherm: 50° C.

The liquid/vapor equilibrium measurements on the HFC-134a/HFO-1234yfbinary mixture are performed for the following isotherm: 20° C.

The liquid/vapor equilibrium measurements on the HFO-1234ze/HFC-263fbbinary mixture are performed for the following isotherm: 30° C.

The liquid/vapor equilibrium measurements on the HFO-1234ze/HFO-1336yfbinary mixture are performed for the following isotherm: 50° C.

The liquid/vapor equilibrium measurements on the HFO-1234ze/HFO-1234yfbinary mixture are performed for the following isotherm: 18° C.

The liquid/vapor equilibrium measurements on the HFO-1234yf/HFO-1336yfbinary mixture are performed for the following isotherm: 50° C.

The liquid/vapor equilibrium measurements on the HFO-1336yf/HFC-263fbbinary mixture are performed for the following isotherm: 50° C.

To evaluate the energy performance qualities, a compression systemequipped with an evaporator and counter-current condenser, a screwcompressor and a depressurizer are considered.

The system functions with 5° C. of overheating. The evaporationtemperature is −5° C. and the condensation temperature is 50° C.

The coefficient of performance (COP) is defined as being the workingpower provided by the system over the power supplied or consumed by thesystem.

The Lorenz coefficient of performance (COPLorenz) is a referencecoefficient of performance. It is temperature dependent and is used tocompare the COPs of the different fluids.

The Lorenz coefficient of performance is defined as follows (thetemperatures T are in K):T _(condenser) ^(mean) =T _(condenser) ^(inlet) −T _(condenser)^(outlet)T _(evaporator) ^(mean) =T _(evaporator) ^(inlet) −T _(evaporator)^(inlet)

The Lorenz COP in the case of conditioned air and refrigeration is:

${COPlorenz} = \frac{T_{evaporator}^{mean}}{T_{condenser}^{mean} - T_{evaporator}^{mean}}$

The Lorenz COP in the case of heating is:

${COPlorenz} = \frac{T_{condenser}^{mean}}{T_{condenser}^{mean} - T_{evaporator}^{mean}}$

For each composition, the coefficient of performance of the Lorenz cycleis calculated as a function of the corresponding temperatures.

In the tables that follow, “Temp (° C.)” denotes the temperature, “P satliquid” denotes the saturating liquid pressure, “P sat vapor” denotesthe saturating vapor pressure, “pressure diff. (%)” denotes the ratio ofthe difference between the saturating liquid pressure and the saturatingvapor pressure, over the saturating liquid pressure (as a %), “Temp evapoutlet” denotes the temperature of the fluid at the evaporator outlet,“Temp comp outlet” denotes the temperature of the fluid at thecompressor outlet, “T cond outlet” denotes the temperature of the fluidat the condenser outlet, “Temp depress inlet” denotes the temperature ofthe fluid at the depressurizer inlet, “evap P (bar)” denotes thepressure of the fluid in the evaporator, “cond P (bar)” denotes thepressure of the fluid in the condenser, “Rate (p/p)” denotes thecompression rate, “Glide” denotes the temperature glide, “% CAP” denotesthe volumetric capacity of the fluid relative to the reference fluidindicated on the first line, “% COP/COPLorenz” denotes the ratio of theCOP for the system relative to the COP for the corresponding Lorenzcycle.

Example 2—Data for the Quasi-Azeotropic Mixtures

HFO-1336yf/HFO-E-1234ze Mixture:

P sat P sat % HFO- HFO- Temp, liq vap pressure 1234ze 1336yf (° C.)(bar) (bar) diff 65 35 −4 1.5 1.3 10.8 70 30 −4 1.5 1.4 9.4 75 25 −4 1.61.4 8.0 80 20 −4 1.6 1.5 6.4 85 15 −5 1.6 1.6 4.8 90 10 −5 1.7 1.6 3.295 5 −5 1.7 1.7 1.5

HFO-1336yf/HFC-134 Mixture:

P sat P sat % HFC- HFO- Temp, liq vap pressure 134 1336yf (° C.) (bar)(bar) diff 60 40 −4 1.6 1.4 10.8 65 35 −4 1.6 1.5 8.7 70 30 −4 1.7 1.66.7 75 25 −5 1.7 1.6 5.0 80 20 −5 1.8 1.7 3.5 85 15 −5 1.8 1.8 2.3 90 10−5 1.8 1.8 1.3 95 5 −5 1.9 1.8 0.6

HFO-1336yf/HFC-134a Mixture:

P sat P sat % HFC- HFO- Temp, liq vap pressure 134a 1336yf (° C.) (bar)(bar) diff 80 20 −4 2.1 1.9 9.9 85 15 −4 2.2 2.1 7.4 90 10 −4 2.3 2.25.0 95 5 −5 2.4 2.3 2.5

HFO-1336yf/HFC-263fb Mixture:

P sat P sat % HFO- HFC- Temp, liq vap pressure 1336yf 263fb (° C.) (bar)(bar) diff 95 5 −5 0.8 0.8 4.4 90 10 −5 0.9 0.8 7.1 85 15 −5 1.0 0.9 8.780 20 −4 1.0 0.9 9.7 75 25 −4 1.1 0.9 10.1 70 30 −4 1.1 1.0 10.1 65 35−4 1.1 1.0 9.9 60 40 −4 1.2 1.1 9.4 55 45 −4 1.2 1.1 8.8 50 50 −4 1.21.1 8.0 45 55 −4 1.3 1.2 7.1 40 60 −4 1.3 1.2 6.2 35 65 −5 1.3 1.2 5.330 70 −5 1.3 1.3 4.3 25 75 −5 1.4 1.3 3.4 20 80 −5 1.4 1.3 2.6 15 85 −51.4 1.4 1.8 10 90 −5 1.4 1.4 1.1 5 95 −5 1.4 1.4 0.5

HFO-1336yf/HFO-1234yf Mixture:

P sat P sat % HFO- HFO- Temp, liq vap pressure 1234yf 1336yf (° C.)(bar) (bar) diff 90 10 −4 2.4 2.2 8.7 95 5 −4 2.5 2.4 4.5

HFO-1336yf/HFO-E-1234ze/HFC-134 Mixture:

P sat P sat % HFO- HFC- HFO- Temp, liq vap pressure 1234ze 134 1336yf (°C.) (bar) (bar) diff 5 60 35 −4 1.6 1.5 9.3 5 65 30 −4 1.7 1.6 7.2 5 7025 −4 1.7 1.6 5.4 5 75 20 −5 1.8 1.7 3.7 5 80 15 −5 1.8 1.8 2.4 5 85 10−5 1.8 1.8 1.3 5 90 5 −5 1.9 1.8 0.6 15 50 35 −4 1.6 1.5 10.5 15 55 30−4 1.7 1.5 8.3 15 60 25 −4 1.7 1.6 6.2 15 65 20 −5 1.8 1.7 4.3 15 70 15−5 1.8 1.7 2.7 15 75 10 −5 1.8 1.8 1.5 15 80 5 −5 1.9 1.8 0.6 25 45 30−4 1.7 1.5 9.3 25 50 25 −4 1.7 1.6 7.1 25 55 20 −5 1.8 1.7 5.0 25 60 15−5 1.8 1.7 3.2 25 65 10 −5 1.8 1.8 1.7 25 70 5 −5 1.9 1.8 0.7 35 35 30−4 1.6 1.5 10.0 35 40 25 −4 1.7 1.6 7.9 35 45 20 −4 1.7 1.6 5.8 35 50 15−5 1.8 1.7 3.8 35 55 10 −5 1.8 1.8 2.1 35 60 5 −5 1.8 1.8 0.9 45 25 30−4 1.6 1.4 10.2 45 30 25 −4 1.7 1.5 8.4 45 35 20 −4 1.7 1.6 6.4 45 40 15−5 1.8 1.7 4.5 45 45 10 −5 1.8 1.8 2.6 45 50 5 −5 1.8 1.8 1.1 55 15 30−4 1.6 1.4 10.0 55 20 25 −4 1.6 1.5 8.5 55 25 20 −4 1.7 1.6 6.8 55 30 15−5 1.7 1.6 4.9 55 35 10 −5 1.8 1.7 3.1 55 40 5 −5 1.8 1.8 1.4 65 5 30 −41.5 1.4 9.6 65 10 25 −4 1.6 1.5 8.2 65 15 20 −4 1.6 1.5 6.7 65 20 15 −51.7 1.6 5.1 65 25 10 −5 1.8 1.7 3.3 65 30 5 −5 1.8 1.8 1.7 75 5 20 −41.6 1.5 6.5 75 10 15 −5 1.7 1.6 5.0 75 15 10 −5 1.7 1.7 3.4 75 20 5 −51.8 1.8 1.7 85 5 10 −5 1.7 1.6 3.2 85 10 5 −5 1.8 1.7 1.7 90 5 5 −5 1.71.7 1.6

HFO-1336yf/HFO-E-1234ze/HFC-134a Mixture:

P sat P sat % HFC- HFO- HFO- Temp, liq vap pressure 134a 1234ze 1336yf(° C.) (bar) (bar) diff 75 5 20 −4 2.1 1.9 9.9 80 5 15 −4 2.2 2.0 7.4 855 10 −4 2.3 2.2 5.0 90 5 5 −5 2.3 2.3 2.6 65 15 20 −4 2.1 1.9 10.2 75 1510 −4 2.2 2.1 5.2 80 15 5 −5 2.3 2.2 2.9 55 25 20 −4 2.0 1.8 10.7 65 2510 −4 2.2 2.1 5.7 70 25 5 −5 2.3 2.2 3.4 55 35 10 −4 2.1 2.0 6.3 60 35 5−5 2.2 2.1 4.0 45 45 10 −4 2.1 1.9 6.8 50 45 5 −5 2.1 2.0 4.5 25 55 20−4 1.8 1.6 10.7 35 55 10 −4 2.0 1.8 7.0 40 55 5 −5 2.1 2.0 4.8 5 65 30−4 1.6 1.4 10.9 15 65 20 −4 1.7 1.6 9.6 25 65 10 −4 1.9 1.8 6.7 30 65 5−5 2.0 1.9 4.8 5 75 20 −4 1.7 1.5 7.7 10 75 15 −4 1.7 1.6 7.0 15 75 10−4 1.8 1.7 5.9 20 75 5 −5 1.9 1.8 4.4 5 85 10 −5 1.7 1.7 4.3 10 85 5 −51.8 1.8 3.4 5 90 5 −5 1.8 1.7 2.6

HFO-1336yf/HFO-E-1234ze/HFC-263fb Mixture:

P sat P sat % HFO- HFO- HFC- Temp, liq vap pressure 1234ze 1336yf 263fb(° C.) (bar) (bar) diff 5 90 5 −5 0.9 0.8 8.2 5 60 35 −4 1.2 1.1 10.4 550 45 −4 1.2 1.1 8.9 5 40 55 −4 1.3 1.2 7.0 5 30 65 −5 1.4 1.3 5.0 5 2075 −5 1.4 1.4 3.1 5 10 85 −5 1.5 1.4 1.4 15 40 45 −4 1.3 1.2 8.4 15 3055 −4 1.4 1.3 6.1 15 20 65 −5 1.4 1.4 3.9 15 10 75 −5 1.5 1.5 2.1 15 580 −5 1.5 1.5 1.3 25 40 35 −4 1.4 1.2 9.6 25 30 45 −4 1.4 1.3 7.1 25 2055 −5 1.5 1.4 4.6 25 10 65 −5 1.5 1.5 2.5 25 5 70 −5 1.5 1.5 1.6 35 3035 −4 1.4 1.3 7.9 35 20 45 −5 1.5 1.4 5.2 35 10 55 −5 1.5 1.5 2.8 35 560 −5 1.6 1.5 1.8 45 30 25 −4 1.5 1.3 8.5 45 20 35 −5 1.5 1.4 5.6 45 1045 −5 1.6 1.5 3.0 45 5 50 −5 1.6 1.6 1.9 55 30 15 −4 1.5 1.4 9.0 55 2025 −4 1.6 1.5 5.9 55 10 35 −5 1.6 1.6 3.0 55 5 40 −5 1.6 1.6 1.8 65 30 5−4 1.5 1.4 9.3 65 20 15 −4 1.6 1.5 6.2 65 10 25 −5 1.6 1.6 3.1 65 5 30−5 1.7 1.6 1.7 75 20 5 −4 1.6 1.5 6.4 75 10 15 −5 1.7 1.6 3.1 75 5 20 −51.7 1.7 1.6 85 10 5 −5 1.7 1.6 3.1 85 5 10 −5 1.7 1.7 1.6 90 5 5 −5 1.71.7 1.5

HFO-1336yf/HFO-E-1234ze/HFO-1234yf Mixture:

P sat P sat % HFO- HFO- HFO- Temp, liq vap pressure 1234yf 1234ze 1336yf(° C.) (bar) (bar) diff 85 5 10 −4 2.4 2.2 8.7 75 15 10 −4 2.3 2.1 9.080 15 5 −4 2.4 2.3 5.1 65 25 10 −4 2.3 2.1 9.3 70 25 5 −4 2.4 2.2 5.7 4545 10 −4 2.1 1.9 9.6 50 45 5 −4 2.2 2.1 6.8 35 55 10 −4 2.0 1.8 9.3 4055 5 −4 2.1 2.0 6.9 15 65 20 −4 1.8 1.6 11.0 25 65 10 −4 1.9 1.8 8.5 3065 5 −4 2.0 1.9 6.6 5 75 20 −4 1.7 1.5 8.2 15 75 10 −4 1.8 1.7 7.0 20 755 −5 1.9 1.8 5.7 5 85 10 −5 1.7 1.7 4.7 10 85 5 −5 1.8 1.8 4.1 5 90 5 −51.8 1.7 3.0

HFO-1336yf/HFO-1234yf/HFC-134a Mixture:

P sat P sat % HFO- HFC- HFO- Temp, liq vap pressure 1234yf 134a 1336yf(° C.) (bar) (bar) diff 85 5 10 −4 2.4 2.2 9.1 90 5 5 −4 2.5 2.4 4.9 7515 10 −4 2.5 2.2 9.4 80 15 5 −4 2.6 2.4 5.1 65 25 10 −4 2.5 2.3 9.3 7025 5 −4 2.6 2.5 5.0 55 35 10 −4 2.5 2.3 8.9 60 35 5 −4 2.6 2.5 4.8 45 4510 −4 2.5 2.3 8.4 50 45 5 −4 2.6 2.5 4.6 35 55 10 −4 2.5 2.3 8.0 40 55 5−5 2.6 2.5 4.4 25 65 10 −4 2.4 2.3 7.4 30 65 5 −5 2.5 2.4 4.3 5 75 20 −42.2 1.9 10.9 15 75 10 −4 2.4 2.2 6.7 20 75 5 −5 2.5 2.4 4.0 5 85 10 −42.3 2.2 5.7 10 85 5 −5 2.4 2.3 3.5 5 90 5 −5 2.4 2.3 3.1

HFO-1336yf/HFC-134/HFC-263fb Mixture:

P sat P sat % HFC- HFO- HFC- Temp, liq vap pressure 134 1336yf 263fb (°C.) (bar) (bar) diff 5 50 45 −4 1.3 1.1 9.8 5 40 55 −4 1.3 1.2 7.7 5 3065 −5 1.4 1.3 5.6 5 20 75 −5 1.4 1.4 3.7 5 10 85 −5 1.5 1.4 2.0 15 40 45−4 1.4 1.2 10.4 15 30 55 −4 1.4 1.3 7.8 15 20 65 −5 1.5 1.4 5.5 15 10 75−5 1.5 1.5 3.5 15 5 80 −5 1.5 1.5 2.7 25 30 45 −4 1.5 1.4 9.2 25 20 55−4 1.6 1.5 6.5 25 10 65 −5 1.6 1.5 4.3 25 5 70 −5 1.6 1.6 3.4 35 30 35−4 1.6 1.4 9.7 35 20 45 −4 1.6 1.5 6.8 35 10 55 −5 1.7 1.6 4.4 35 5 60−5 1.7 1.6 3.4 45 30 25 −4 1.6 1.5 9.4 45 20 35 −4 1.7 1.6 6.5 45 10 45−5 1.7 1.6 4.0 45 5 50 −5 1.7 1.7 3.0 55 30 15 −4 1.7 1.5 8.5 55 20 25−4 1.7 1.6 5.6 55 10 35 −5 1.8 1.7 3.3 55 5 40 −5 1.8 1.7 2.3 65 30 5 −41.7 1.6 7.3 65 20 15 −5 1.7 1.7 4.6 65 10 25 −5 1.8 1.7 2.4 65 5 30 −51.8 1.8 1.5 75 20 5 −5 1.8 1.7 3.8 75 10 15 −5 1.8 1.8 1.7 75 5 20 −51.8 1.8 1.0 85 10 5 −5 1.8 1.8 1.4 85 5 10 −5 1.8 1.8 0.7 90 5 5 −5 1.91.8 0.6

HFO-1336yf/HFC-134a/HFC-263fb Mixture:

P sat P sat % HFC- HFO- HFC- Temp, liq vap pressure 134a 1336yf 263fb (°C.) (bar) (bar) diff 5 40 55 −4 1.3 1.2 8.8 5 30 65 −4 1.4 1.3 6.6 5 2075 −5 1.4 1.4 4.6 5 10 85 −5 1.5 1.4 2.9 15 20 65 −4 1.5 1.4 7.9 15 1075 −5 1.6 1.5 5.7 15 5 80 −5 1.6 1.5 4.8 25 20 55 −4 1.6 1.5 10.3 25 1065 −4 1.7 1.6 7.7 25 5 70 −4 1.7 1.6 6.6 35 10 55 −4 1.8 1.6 8.8 35 5 60−4 1.8 1.7 7.5 45 10 45 −4 1.9 1.7 9.0 45 5 50 −4 1.9 1.8 7.7 55 10 35−4 2.0 1.8 8.6 55 5 40 −4 2.0 1.9 7.2 65 10 25 −4 2.1 1.9 7.6 65 5 30 −42.1 2.0 6.2 75 20 5 −4 2.1 1.9 10.2 75 10 15 −4 2.2 2.0 6.3 75 5 20 −52.2 2.1 4.9 85 10 5 −4 2.3 2.1 5.3 85 5 10 −5 2.3 2.2 3.5 90 5 5 −5 2.32.3 2.9

Example 3—Results for a Moderate-Temperature Refrigeration, Comparisonwith HFO-1234ze

Temp Temp Temp evap comp T cond depress evap P cond P Rate glide comp %COP/ outlet (° C.) outlet (° C.) outlet (° C.) inlet (° C.) (bar) (bar)(p/p) (° C.) yield % CAP COPLorenz HFO-1234ze −5 62 50 45 1.8 10.0 5.60.0 76 100 58 HFC- HFC- HFO- 134a 134 1336yf 0 75 25 −5 63 49 44 2 9.95.8 1.0 75.5 100 59 0 80 20 −5 64 50 45 2 10.1 5.8 0.7 75.6 103 60 0 8515 −5 65 50 45 2 10.2 5.7 0.4 75.6 105 60 0 90 10 −5 66 50 45 2 10.4 5.70.3 75.7 108 61 0 95 5 −5 66 50 45 2 10.5 5.7 0.1 75.7 110 62 65 0 35 −365 48 43 2 10.4 5.6 4 75.9 104 58 70 0 30 −3 65 48 43 2 10.7 5.6 3 76.0109 59 75 0 25 −4 66 48 43 2 11.1 5.5 3 76.1 114 60 80 0 20 −4 67 49 442 11.5 5.5 2 76.2 119 60 85 0 15 −4 68 49 44 2 11.9 5.5 2 76.3 123 61 900 10 −4 69 49 44 2 12.3 5.4 1 76.4 128 62 95 0 5 −5 70 50 45 2 12.7 5.41 76.4 133 63 5 70 25 −4 63.18 49 44 2 9.9 6 1.0 75.5 98 58 5 75 20 −563.83 50 45 2 10.1 6 0.7 75.6 102 59 5 80 15 −5 64.55 50 45 2 10.2 6 0.575.6 104 60 5 85 10 −5 65.34 50 45 2 10.4 6 0.3 75.7 108 61 5 90 5 −566.13 50 45 2 10.5 6 0.1 75.7 110 62 15 70 15 −5 64.09 50 45 2 10.2 60.5 75.6 102 59 15 75 10 −5 64.85 50 45 2 10.4 6 0.3 75.8 106 60 15 80 5−5 65.64 50 45 2 10.5 6 0.1 75.7 109 61 25 60 15 −5 63.64 50 45 2 10.2 60.6 75.7 101 58 25 65 10 −5 64.42 50 45 2 10.4 6 0.3 75.7 105 59 25 70 5−5 65.18 50 45 2 10.5 6 0.1 75.7 108 60 35 55 10 −5 64.04 50 45 2 10.3 60.4 75.7 103 58 35 60 5 −5 64.74 50 45 2 10.5 6 0.2 75.7 107 60 45 45 10−5 63.68 50 45 2 10.2 6 0.5 75.7 101 58 45 50 5 −5 64.23 50 45 2 10.4 60.2 75.8 106 59 55 35 10 −5 63.24 50 45 2 10.1 6 0.6 75.7 100 57 55 40 5−5 63.81 50 45 2 10.4 6 0.3 75.8 104 59 65 30 5 −5 63.37 50 45 2 10.2 60.3 75.8 103 58 75 20 5 −5 62.86 50 45 2 10.1 6 0.3 75.7 101 58 85 10 5−5 62.3 50 45 2 9.9 6 0.3 75.8 99 58 60 5 35 −3 64.24 48 43 2 10.3 6 3.675.8 102 57 65 5 30 −3 65.03 48 43 2 10.7 6 3.1 76.0 107 58 70 5 25 −465.81 48 43 2 11.1 6 2.6 76.1 111 59 75 5 20 −4 66.61 49 44 2 11.4 5 2.176.2 116 59 80 5 15 −4 67.46 49 44 2 11.8 5 1.5 76.3 119 59 85 5 10 −468.28 49 44 2 12.2 5 1.0 76.3 125 61 90 5 5 −5 69.36 50 45 2 12.6 5 0.576.4 131 62 55 15 30 −3 64.35 48 43 2 10.5 6 3.0 75.9 102 56 65 15 20 −465.92 49 44 2 11.3 6 2.0 76.1 111 57 75 15 10 −4 67.56 49 44 2 12.1 51.0 76.3 119 59 80 15 5 −5 68.6 50 45 2 12.5 5 0.6 76.3 128 61 55 25 20−4 65.33 49 44 2 11.0 6 2.1 76.0 107 56 65 25 10 −4 67.08 49 44 2 11.8 61.1 76.1 113 57 70 25 5 −5 67.91 50 45 2 12.2 5 0.7 76.2 124 60 45 35 20−4 64.73 49 44 2 10.8 6 2.1 75.8 104 56 55 35 10 −4 66.47 49 44 2 11.6 61.2 76.0 108 55 60 35 5 −5 67.25 49 44 2 12.0 6 0.8 76.1 120 60 35 45 20−4 64.04 49 44 2 10.5 6 2.1 75.7 101 56 45 45 10 −4 65.82 49 44 2 11.3 61.2 75.9 103 54 50 45 5 −5 66.56 49 44 2 11.7 6 0.8 76.0 116 59 35 55 10−4 65.07 49 44 2 10.9 6 1.2 75.8 101 54 40 55 5 −5 65.79 49 44 2 11.4 60.9 75.9 113 59 25 65 10 −4 64.18 49 44 2 10.6 6 1.2 75.7 101 56 30 65 5−5 64.93 49 44 2 11.0 6 0.8 75.9 109 58 15 75 10 −4 63.16 49 44 2 10.2 61.0 75.7 100 57 20 75 5 −5 63.97 49 44 2 10.6 6 0.8 75.8 105 58 10 85 5−5 62.89 50 45 2 10.2 6 0.6 75.8 102 58 75 0 25 −3 57.94 48 43 2 10.7 53.8 76.5 103 53 80 0 20 −3 58 48 43 2 11.1 5 3.3 76.7 107 53 85 0 15 −457.95 49 44 2 11.6 5 2.6 77.0 112 53 90 0 10 −4 57.81 49 44 2 12.0 5 1.977.2 116 53 95 0 5 −4 57.56 50 45 2 12.4 5 1.0 77.4 121 54 75 5 20 −358.02 48 43 2 11.1 5 3.2 76.7 106 53 85 5 10 −4 58.08 49 44 2 11.9 5 1.977.1 115 53 65 15 20 −3 58.69 48 43 2 10.9 5 3.1 76.5 105 53 75 15 10 −458.65 49 44 2 11.8 5 1.9 76.9 113 53 80 15 5 −4 58.47 50 45 2 12.2 5 1.177.1 119 54 55 25 20 −4 59.16 48 43 2 10.8 5 3.0 76.3 103 53 65 25 10 −459.2 49 44 2 11.6 5 1.9 76.7 110 53 70 25 5 −4 58.97 50 45 2 12.0 5 1.276.9 117 54 45 35 20 −4 59.57 48 43 2 10.5 6 2.8 76.1 100 54 55 35 10 −459.74 49 44 2 11.4 5 1.8 76.5 106 52 60 35 5 −4 59.68 49 44 2 11.8 5 1.276.7 115 55 45 45 10 −4 60.12 49 44 2 11.1 5 1.7 76.3 103 53 50 45 5 −460.24 49 44 2 11.5 5 1.3 76.6 113 55 35 55 10 −4 60.63 49 44 2 10.8 61.7 76.2 104 54 40 55 5 −4 60.73 49 44 2 11.2 5 1.2 76.4 110 56 25 65 10−4 60.94 49 44 2 10.5 6 1.5 76.0 102 56 30 65 5 −4 61.13 49 44 2 10.9 51.1 76.2 107 56 15 75 10 −4 61.06 49 44 2 10.1 6 1.2 75.9 100 56 20 75 5−5 61.43 49 44 2 10.6 6 0.9 76.0 104 56 10 85 5 −5 61.49 50 45 2 10.2 60.7 75.9 101 57 75 5 20 −3 58.41 48 43 2 11.2 5 3.4 76.8 108 53 85 5 10−4 58.18 49 44 2 12.1 5 2.0 77.2 118 54 90 5 5 −4 57.91 50 45 3 12.5 51.1 77.4 123 54 55 15 30 −3 59.31 47 42 2 10.6 5 4.4 76.4 101 53 65 1520 −3 59.37 48 43 2 11.4 5 3.5 76.8 110 54 75 15 10 −4 59.08 49 44 212.2 5 2.1 77.2 120 54 80 15 5 −4 58.74 50 45 3 12.7 5 1.1 77.5 125 5545 25 30 −3 60.48 47 42 2 10.7 5 4.4 76.3 103 54 55 25 20 −3 60.46 48 432 11.5 5 3.4 76.7 112 54 65 25 10 −4 60.16 49 44 2 12.4 5 2.0 77.2 12255 70 25 5 −4 59.81 50 45 3 12.8 5 1.1 77.4 127 55 35 35 30 −3 61.69 4742 2 10.8 5 4.3 76.2 105 55 45 35 20 −3 61.47 48 43 2 11.7 5 3.3 76.7114 55 55 35 10 −4 61.37 49 44 2 12.5 5 2.0 77.1 124 56 60 35 5 −4 61 5045 3 12.9 5 1.1 77.3 129 56 25 45 30 −3 62.98 48 43 2 10.9 6 4.0 76.1107 56 35 45 20 −3 62.72 48 43 2 11.8 5 3.1 76.5 116 56 45 45 10 −462.69 49 44 2 12.6 5 1.8 77.0 126 57 50 45 5 −4 62.33 50 45 3 13.0 5 1.077.2 131 57 15 55 30 −3 63.93 48 43 2 10.9 6 3.8 76.1 108 57 25 55 20 −464.09 48 43 2 11.8 5 2.9 76.4 118 58 35 55 10 −4 64.07 49 44 2 12.6 51.7 76.9 127 58 40 55 5 −5 63.76 50 45 3 13.0 5 1.0 77.1 132 58 5 65 30−3 64.82 48 43 2 10.8 6 3.4 76.0 109 58 15 65 20 −4 65.32 48 43 2 11.7 52.6 76.3 119 59 25 65 10 −4 65.46 49 44 2 12.6 5 1.6 76.7 128 59 30 65 5−5 65.25 50 45 3 13.0 5 0.9 76.9 133 59 5 75 20 −4 66.57 49 44 2 11.6 52.3 76.2 119 60 15 75 10 −4 66.8 49 44 2 12.5 5 1.4 76.6 129 60 20 75 5−5 66.77 50 45 2 13.0 5 0.8 76.7 134 61 5 85 10 −4 68.07 49 44 2 12.4 51.2 76.4 129 62 10 85 5 −5 68.23 50 45 2 12.9 5 0.7 76.6 134 62 5 90 5−5 69.02 50 45 2 12.8 5 0.6 76.5 133 62 45 5 50 −5 62.67 49 44 2 9.6 60.5 75.9 98 59 55 10 35 −5 63.07 50 45 2 9.8 6 0.6 75.8 100 59 55 5 40−5 63.38 50 45 2 9.9 6 0.4 75.9 101 59 65 20 15 −5 63.22 49 44 2 9.9 60.9 75.6 100 59 65 10 25 −5 63.82 50 45 2 10.1 6 0.5 75.7 103 60 65 5 30−5 64.06 50 45 2 10.2 6 0.3 75.9 105 60 75 20 5 −5 63.91 50 45 2 10.1 60.7 75.6 102 59 75 10 15 −5 64.49 50 45 2 10.3 6 0.3 75.7 106 60 75 5 20−5 64.85 50 45 2 10.4 6 0.2 75.8 107 61 85 10 5 −5 65.13 50 45 2 10.4 60.3 75.7 108 61 85 5 10 −5 65.58 50 45 2 10.5 6 0.1 75.8 109 61 90 5 5−5 65.88 50 45 2 10.5 6 0.1 75.7 110 62 35 5 60 −4 63.28 49 44 2 9.7 61.3 76.1 99 59 45 20 35 −4 63.9 48 43 2 10.0 6 2.2 75.8 101 58 45 10 45−4 64.3 49 44 2 10.2 6 1.6 76.0 104 59 45 5 50 −4 64.53 49 44 2 10.2 61.4 76.1 105 59 55 30 15 −3 64.44 48 43 2 10.3 6 3.1 75.7 102 58 55 2025 −4 65.08 48 43 2 10.5 6 2.3 75.9 106 59 55 10 35 −4 65.49 49 44 210.7 6 1.6 76.0 109 60 55 5 40 −4 65.71 49 44 2 10.8 6 1.3 76.1 111 6065 30 5 −3 65.26 48 43 2 10.6 6 3.1 75.9 107 58 65 20 15 −4 65.99 49 442 11.0 6 2.2 76.0 111 59 65 10 25 −4 66.58 49 44 2 11.2 6 1.5 76.1 11560 65 5 30 −4 66.82 49 44 2 11.3 6 1.2 76.2 116 61 75 20 5 −4 66.78 4944 2 11.4 6 2.1 76.1 116 60 75 10 15 −4 67.56 49 44 2 11.7 6 1.3 76.2121 61 75 5 20 −5 67.86 49 44 2 11.8 5 1.0 76.2 122 61 85 10 5 −4 68.4249 44 2 12.2 5 1.1 76.3 126 62 85 5 10 −5 68.71 50 45 2 12.3 5 0.7 76.3128 62 90 5 5 −5 69.26 50 45 2 12.5 5 0.6 76.3 131 63

The invention claimed is:
 1. A quasi-azeotropic composition consistingof: a mixture of 5-30% by weight of 2,3,3,4,4,4-hexafluorobut-1-ene and70-95% by weight of trans-1,3,3,3-tetrafluoropropene, wherein thedifference between the liquid saturation pressure and the vaporsaturation pressure at a temperature of −5° C. is less than or equal to10% of the liquid saturation pressure.
 2. The composition as claimed inclaim 1, which is non-flammable.
 3. A heat-transfer composition,comprising the composition as claimed in claim 1 as heat-transfer fluid,and also one or more additives chosen from lubricants, stabilizers,surfactants, tracers, fluorescers, odorous agents and solubilizers, andmixtures thereof.
 4. A heat transfer installation comprising a vaporcompression circuit containing a composition as claimed in claim 1 asheat-transfer fluid optionally with one or more additives chosen fromlubricants, stabilizers, surfactants, tracers, fluorescers, odorousagents and solubilizers, and mixtures thereof.
 5. The installation asclaimed in claim 4, chosen from mobile or stationary heat-pump heating,air-conditioning, refrigeration, freezing and Rankine cycleinstallations.
 6. A process for heating or cooling a fluid or a body bymeans of a vapor compression circuit containing a heat-transfer fluid,said process successively comprising the evaporation of theheat-transfer fluid, the compression of the heat-transfer fluid, thecondensation of the heat fluid and the depressurization of theheat-transfer fluid, in which the heat-transfer fluid is a compositionas claimed in claim
 1. 7. The process as claimed in claim 6, which is aprocess for cooling a fluid or a body, in which the temperature of thecooled fluid or body is from −15° C. to 15° C.; or which is a processfor heating a fluid or a body, in which the temperature of the heatedfluid or body is from 30° C. to 90° C.
 8. A process for reducing theenvironmental impact of a heat-transfer installation comprising a vaporcompression circuit containing an initial heat-transfer fluid, saidprocess comprising a step of replacing the initial heat-transfer fluidin the vapor compression circuit with a final transfer fluid, the finaltransfer fluid having a lower GWP than the initial heat-transfer fluid,in which the final heat-transfer fluid is a composition as claimed inclaim
 1. 9. A quasi-azeotropic composition consisting of: a mixture of5-30% by weight of 2,3,3,4,4,4-hexafluorobut-1-ene and 70-95% by weightof trans-1,3,3,3-tetrafluoropropene.
 10. The quasi-azeotropiccomposition as claimed in claim 9, which is non-flammable.
 11. Aheat-transfer composition, comprising the quasi-azeotropic compositionas claimed in claim 9 as heat-transfer fluid, and also one or moreadditives chosen from lubricants, stabilizers, surfactants, tracers,fluorescers, odorous agents and solubilizers, and mixtures thereof. 12.A heat transfer installation comprising a vapor compression circuitcontaining a quasi-azeotropic composition as claimed in claim 9 asheat-transfer fluid optionally with one or more additives chosen fromlubricants, stabilizers, surfactants, tracers, fluorescers, odorousagents and solubilizers, and mixtures thereof.
 13. The installation asclaimed in claim 12, chosen from mobile or stationary heat-pump heating,air-conditioning, refrigeration, freezing and Rankine cycleinstallations.
 14. A process for heating or cooling a fluid or a body bymeans of a vapor compression circuit containing a heat-transfer fluid,said process successively comprising the evaporation of theheat-transfer fluid, the compression of the heat-transfer fluid, thecondensation of the heat fluid and the depressurization of theheat-transfer fluid, in which the heat-transfer fluid is aquasi-azeotropic composition as claimed in claim
 9. 15. The process asclaimed in claim 14, which is a process for cooling a fluid or a body,in which the temperature of the cooled fluid or body is from −15° C. to15° C.; or which is a process for heating a fluid or a body, in whichthe temperature of the heated fluid or body is from 30° C. to 90° C. 16.A process for reducing the environmental impact of a heat-transferinstallation comprising a vapor compression circuit containing aninitial heat-transfer fluid, said process comprising a step of replacingthe initial heat-transfer fluid in the vapor compression circuit with afinal transfer fluid, the final transfer fluid having a lower GWP thanthe initial heat-transfer fluid, in which the final heat-transfer fluidis a composition as claimed in claim 9.